JP4032248B2 - Combustion catalyst for automobile exhaust gas purification - Google Patents
Combustion catalyst for automobile exhaust gas purification Download PDFInfo
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- JP4032248B2 JP4032248B2 JP2003122622A JP2003122622A JP4032248B2 JP 4032248 B2 JP4032248 B2 JP 4032248B2 JP 2003122622 A JP2003122622 A JP 2003122622A JP 2003122622 A JP2003122622 A JP 2003122622A JP 4032248 B2 JP4032248 B2 JP 4032248B2
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- combustion catalyst
- exhaust gas
- calcium silicate
- copper
- automobile exhaust
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/204—Alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20761—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/30—Silica
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
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- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Exhaust Gas After Treatment (AREA)
Description
【０００１】
【発明の属する技術分野】
【０００２】
本発明は、自動車排ガス浄化用燃焼触媒に関する。本明細書における自動車には、自動二輪車及び原動機付き自転車も含まれる。
【従来の技術】
【０００３】
従来、自動車の排ガスを浄化するための燃焼触媒が種々開発されている。例えば、アルミナ等の担体に触媒活性を有する白金、ロジウム、パラジウム等の貴金属を担持してなる燃焼触媒が知られている。
【０００４】
具体的には、例えば、特許文献１には、触媒担体上に白金、パラジウム及びロジウムからなる群から選ばれた少なくとも１種の貴金属を含有する活性アルミナを主成分とした第１コート層を設け、該第１コート層上に貴金属成分を含まない活性アルミナを主成分とした無機物から成る第２コート層を設け、該第２コート層上に金属をイオン交換したゼオライト粉末を主成分とした無機物から成る第３コート層を設けてなる触媒を触媒コンバーターの上流側に配置し、三元触媒を前記コンバーターの下流側に配置したことを特徴とする排ガス浄化用触媒が開示されている。
【０００５】
既存の燃焼触媒の中でも、特に上記のような貴金属を活性成分とする燃焼触媒は、排ガス浄化活性が高いことが知られている。しかしながら、このような燃焼触媒は、貴金属成分が高価であるためコストが高いという問題がある。特に、担体としてアルミナ等を用いる場合には、更に燃焼触媒のコストが高くなる。
【０００６】
従って、従来品よりも安価で且つ排ガス浄化活性の高い燃焼触媒の開発が望まれている。
【特許文献１】
特開平７−２５６１１３号公報
【発明が解決しようとする課題】
【０００７】
本発明は、従来品よりも安価で且つ排ガス浄化活性の高い燃焼触媒を提供することを主な目的とする。
【課題を解決するための手段】
【０００８】
本発明者は、上記目的を達成すべく鋭意研究を重ねた結果、珪酸カルシウムとＣｕＣ ２ Ｏ ４ ・１／２Ｈ ２ Ｏとを反応させる工程を経ることにより得られる、特定の無機材料及び銅化合物を含んでなる材料が上記目的を達成できることを見出し、本発明を完成するに至った。
【０００９】
即ち、本発明は、下記の自動車排ガス浄化用燃焼触媒及びその製造方法に係るものである。
１．珪酸カルシウムとＣｕＣ ２ Ｏ ４ ・１／２Ｈ ２ Ｏとを反応させることにより得られる、カルシウム塩、非晶質シリカ及び銅化合物を含むことを特徴とする自動車排ガス浄化用燃焼触媒（第１発明）。
２．珪酸カルシウムとＣｕＣ ２ Ｏ ４ ・１／２Ｈ ２ Ｏとを反応させて得られた反応生成物を水洗するか、又は酸処理もしくは銅塩水溶液による処理を経て水洗することにより得られる、非晶質シリカ及び銅化合物を含むことを特徴とする自動車排ガス浄化用燃焼触媒（第２発明）。
３．珪酸カルシウムとＣｕＣ ２ Ｏ ４ ・１／２Ｈ ２ Ｏとを反応させて得られた反応生成物を 焼成することにより得られる、結晶質シリカ及び非晶質シリカの少なくとも１種、カルシウム塩並びに銅酸化物を含むことを特徴とする自動車排ガス浄化用燃焼触媒（第３発明）。
４．珪酸カルシウムとＣｕＣ ２ Ｏ ４ ・１／２Ｈ ２ Ｏとを反応させて得られた反応生成物を水洗するか、又は酸処理もしくは銅塩水溶液による処理を経て水洗した後、更に焼成することにより得られる、結晶質シリカ及び非晶質シリカの少なくとも１種並びに銅酸化物を含むことを特徴とする自動車排ガス浄化用燃焼触媒（第４発明）。
５．珪酸カルシウムとＣｕＣ ２ Ｏ ４ ・１／２Ｈ ２ Ｏとを反応させて得られた反応生成物を焼成後、更に水洗するか、又は酸処理もしくは銅塩水溶液による処理を経て水洗することにより得られる、結晶質シリカ及び非晶質シリカの少なくとも１種並びに銅酸化物を含むことを特徴とする自動車排ガス浄化用燃焼触媒（第４発明）。
６．銅化合物がＸ線回折図形の２θ＝２３．５°及び２θ＝３１．０°にピークを有する、上記項１又は２に記載の自動車排ガス浄化用燃焼触媒。
７．珪酸カルシウムとＣｕＣ ２ Ｏ ４ ・１／２Ｈ ２ Ｏとを反応させることを特徴とする上記項１に記載の自動車排ガス浄化用燃焼触媒の製造方法。
８．珪酸カルシウムとＣｕＣ ２ Ｏ ４ ・１／２Ｈ ２ Ｏとを反応させて得られた反応生成物を水洗するか、又は酸処理もしくは銅塩水溶液による処理を経て水洗することを特徴とする上記項２に記載の自動車排ガス浄化用燃焼触媒の製造方法。
９．珪酸カルシウムとＣｕＣ ２ Ｏ ４ ・１／２Ｈ ２ Ｏとを反応させて得られた反応生成物を焼成することを特徴とする上記項３に記載の自動車排ガス浄化用燃焼触媒の製造方法。
１０．珪酸カルシウムとＣｕＣ ２ Ｏ ４ ・１／２Ｈ ２ Ｏとを反応させて得られた反応生成物を水洗するか、又は酸処理もしくは銅塩水溶液による処理を経て水洗した後、更に焼成することを特徴とする上記項４に記載の自動車排ガス浄化用燃焼触媒の製造方法。
１１．珪酸カルシウムとＣｕＣ ２ Ｏ ４ ・１／２Ｈ ２ Ｏとを反応させて得られた反応生成物を焼成後、更に水洗するか、又は酸処理もしくは銅塩水溶液による処理を経て水洗することを特徴とする上記項５に記載の自動車排ガス浄化用燃焼触媒の製造方法。
【発明の実施の形態】
【００１０】
第１発明の自動車排ガス浄化用燃焼触媒
第１発明の燃焼触媒は、カルシウム塩、非晶質シリカ及び銅化合物を含む。
【００１１】
燃焼触媒中のカルシウム塩、非晶質シリカ及び銅化合物の含有割合は特に限定されず、用いる原料の種類等に応じて異なるが、例えば、後記の製造方法で示した範囲から、最終製品の目的、所望の性能等に応じて適宜設定できる。
【００１２】
燃焼触媒には、上記３成分の他、燃焼触媒活性を妨げない範囲において添加剤が含まれていてもよい。添加剤としては特に限定されず、燃焼触媒の分野で公知のものが使用できる。添加剤の種類、配合量等は、最終製品の目的、所望の性能等に応じて適宜設定できる。
【００１３】
製造方法
燃焼触媒の製造方法としては、珪酸カルシウムと銅塩（ＣｕＣ ２ Ｏ ４ ・１／２Ｈ ２ Ｏ）とを反応させる方法を用いる。以下、本製造方法について説明する。
【００１４】
珪酸カルシウムとしては特に限定されず、合成珪酸カルシウム又は天然珪酸カルシウムのいずれでもよいが、反応性、成形性等を考慮すると、合成珪酸カルシウムが好ましい。
【００１５】
合成珪酸カルシウムとしては、石灰原料と珪酸原料とから水熱反応により得られるもの、例えば、ゾノトライト、トベルモライト、フォシャジャイト、ジャイロライト、α−ダイカルシウムシリケート、トリカルシウムシリケート、ヒレブランダイト、ローゼンハナイト、トラスコタイト、リエライト、カルシオコンドロダイト、キルコアナイト、アフィライト等が挙げられる。また、準結晶質珪酸カルシウム（ＣＳＨｎ）等の合成珪酸カルシウム水和物、上記ゾノトライト、トベルモライト等の合成珪酸カルシウム水和物を加熱して得られるワラストナイト等も挙げられる。
【００１６】
銅塩としては、ＣｕＣ２Ｏ４・１／２Ｈ２Ｏ（シュウ酸銅）を用いる。シュウ酸銅を用いる場合には、排ガス浄化活性の高い燃焼触媒が得られ易い。
【００１７】
珪酸カルシウムと銅塩とを反応させる方法は特に限定されない。例えば、珪酸カルシウムの水性スラリーに銅塩を混合する方法、珪酸カルシウムの成形体に銅塩の溶液を含浸させる方法、珪酸カルシウムの粉粒体を銅塩の溶液に混合する方法等が挙げられる。
【００１８】
珪酸カルシウムと反応させる銅塩の量は特に限定されず、最終製品の目的、所望の性能等を考慮して適宜設定できる。銅塩の量は、珪酸カルシウムに対して反応当量でもよく、それを超える量でもよく、或いは当量未満でもよい。
【００１９】
珪酸カルシウムと銅塩（ＣｕＣ ２ Ｏ ４ ・１／２Ｈ ２ Ｏ）との反応により、ＣａＣ２Ｏ４・Ｈ２Ｏ、ＣａＣ２Ｏ４等のカルシウム塩；非晶質シリカ；図１に示すようなＸ線回折図形の２θ＝２３．５°付近及び２θ＝３１．０°付近にピークを有する銅化合物等が得られる。
【００２０】
珪酸カルシウムに対して反応当量未満の銅塩を用いた場合には、反応生成物に未反応珪酸カルシウムが残存する場合があるが触媒性能上支障はない。珪酸カルシウム成形体の表層部だけが銅塩と反応した場合でも触媒性能上支障はない。
【００２１】
このようにして得られた反応生成物（珪酸カルシウムの粉粒体を銅塩の溶液と反応させる場合には、反応後の懸濁液をろ過して得たもの）を、必要に応じて成形等により所望の形状とし、また必要に応じて乾燥等することにより、所定のカルシウム塩、非晶質シリカ及び銅化合物を含む燃焼触媒が得られる。
【００２２】
前記で説明した方法により得られる燃焼触媒中の所定成分の含有割合は特に限定的ではないが、燃焼触媒１００重量％中、通常、カルシウム塩１〜５０重量％程度、非晶質シリカ１〜３０重量％程度、銅化合物２〜８５重量％程度である。但し、各成分の含有割合は、燃焼触媒の所望の性能等に応じて適宜設定でき、必ずしも上記範囲に限定されない。
【００２３】
反応生成物の成形方法としては特に限定されないが、例えば、プレス成形法、押出成形法、鋳型成形法、抄造法、造粒法等が挙げられる。必要に応じて、成形時に加熱してもよく、成形後に乾燥、水蒸気養生等をしてもよい。また成形体を粉砕して粉末状にしてもよい。
【００２４】
第２発明の自動車排ガス浄化用燃焼触媒
第２発明の燃焼触媒は、非晶質シリカ及び銅化合物を含む。
【００２５】
燃焼触媒中の非晶質シリカ及び銅化合物の含有割合は特に限定されず、用いる原料の種類等に応じて異なるが、例えば、後記の製造方法で示した範囲から、最終製品の目的、所望の性能等に応じて適宜設定できる。
【００２６】
燃焼触媒には、上記２成分の他、燃焼触媒活性を妨げない範囲において添加剤が含まれていてもよい。添加剤としては特に限定されず、燃焼触媒の分野で公知のものが使用できる。添加剤の種類、配合量等は、最終製品の目的、所望の性能等に応じて適宜設定できる。
【００２７】
製造方法
燃焼触媒の製造方法としては、珪酸カルシウムと銅塩（ＣｕＣ ２ Ｏ ４ ・１／２Ｈ ２ Ｏ）とを反応させて得られた反応生成物を水洗するか、又は酸処理もしくは銅塩水溶液による処理を経て水洗する方法を用いる。以下、本製造方法について説明する。
【００２８】
珪酸カルシウム及び銅塩（ＣｕＣ ２ Ｏ ４ ・１／２Ｈ ２ Ｏ）としては特に限定されず、第１発明の燃焼触媒において説明したものと同じものが使用できる。
【００２９】
珪酸カルシウムと銅塩とを反応させる方法及び珪酸カルシウムと反応させる銅塩の量も特に限定されず、第１発明の燃焼触媒において説明した方法及び量に倣って設定できる。
【００３０】
珪酸カルシウムと銅塩との反応により、第１発明の燃焼触媒において説明したような反応生成物、即ちカルシウム塩、非晶質シリカ及び銅化合物を含む反応生成物が得られる。
【００３１】
珪酸カルシウムに対して反応当量未満の銅塩を用いた場合には、反応生成物に未反応珪酸カルシウムが残存する場合があるが触媒性能上支障はない。珪酸カルシウム成形体の表層部だけが銅塩と反応した場合でも触媒性能上支障はない。
【００３２】
次いで、反応生成物を水洗するか、又は酸処理もしくは銅塩水溶液による処理を経て水洗する。水洗、又は酸処理もしくは銅塩水溶液による処理を経て水洗する条件としては、反応生成物に含まれるカルシウム塩を充分に水溶化して除去できる限り特に限定されない。
【００３３】
水洗する際には、反応生成物を水と接触させればよい。
【００３４】
酸処理には、例えば、硫酸、硝酸、塩酸、酢酸等の酸処理液が使用できる。酸処理液の濃度は特に限定されないが、通常１〜１２規定、好ましくは３〜８規定程度である。酸処理の際には、反応生成物と酸処理液とを接触させればよい。
【００３５】
銅塩水溶液による処理には、例えば、銅の硫酸塩、硝酸塩、酢酸塩、塩化物等の水溶液が使用できる。銅塩水溶液の濃度は特に限定されないが、通常２〜３０重量％、好ましくは３〜１０重量％程度である。処理の際には、反応生成物と当該水溶液とを接触させればよい。
【００３６】
これら酸処理又は銅塩水溶液による処理は、例えば、珪酸カルシウムと反応させる銅塩としてシュウ酸銅を用いる場合に有効である。この理由は、次の通りである。シュウ酸銅と珪酸カルシウムとの反応により得られるシュウ酸カルシウムは水に難溶性であるため、水洗だけではシュウ酸カルシウムは十分に除去できない。しかしながら、酸処理又は銅塩水溶液による処理、例えば、硫酸銅水溶液との接触により、シュウ酸カルシウムを水溶性の硫酸カルシウムに変えれば、後の水洗によりこれを除去できるからである。
【００３７】
これら酸処理又は銅塩水溶液による処理後は、反応生成物を水洗する。中性となるまで水洗することが好ましい。これらの処理条件によっては、不可避的にわずかなカルシウム塩が反応生成物に残存する場合があるが、触媒性能上特に支障はない。
【００３８】
前記で説明した方法により得られる燃焼触媒中の所定成分の含有割合は特に限定的ではないが、燃焼触媒１００重量％中、通常、非晶質シリカ０．５〜４０重量％程度、銅化合物３〜９５重量％程度である。但し、各成分の含有割合は、燃焼触媒の所望の性能等に応じて適宜設定でき、必ずしも上記範囲に限定されない。
【００３９】
反応生成物の成形方法としては特に限定されず、第１発明の燃焼触媒において説明した方法が採用できる。但し、水洗、又は酸処理もしくは銅塩水溶液による処理は成形の前に行う方が好ましい。
【００４０】
第３発明の自動車排ガス浄化用燃焼触媒
第３発明の燃焼触媒は、結晶質シリカ及び非晶質シリカの少なくとも１種、カルシウム塩並びに銅酸化物を含む。
【００４１】
燃焼触媒中の結晶質シリカ及び非晶質シリカの少なくとも１種、カルシウム塩並びに銅酸化物の含有割合は特に限定されず、用いる原料の種類等に応じて異なるが、例えば、後記の製造方法で示した範囲から、最終製品の目的、所望の性能等に応じて適宜設定できる。
【００４２】
燃焼触媒には、上記３成分（結晶質シリカ及び非晶質シリカはまとめてシリカ１成分とする）の他、燃焼触媒活性を妨げない範囲において添加剤が含まれていてもよい。添加剤としては特に限定されず、燃焼触媒の分野で公知のものが使用できる。添加剤の種類、配合量等は、最終製品の目的、所望の性能等に応じて適宜設定できる。
【００４３】
製造方法
燃焼触媒の製造方法としては、珪酸カルシウムと銅塩（ＣｕＣ ２ Ｏ ４ ・１／２Ｈ ２ Ｏ）とを反応させて得られた反応生成物を焼成する方法を用いる。以下、本製造方法について説明する。
【００４４】
珪酸カルシウム及び銅塩（ＣｕＣ ２ Ｏ ４ ・１／２Ｈ ２ Ｏ）としては特に限定されず、第１発明の燃焼触媒において説明したものと同じものが使用できる。
【００４５】
珪酸カルシウムと銅塩とを反応させる方法及び珪酸カルシウムと反応させる銅塩の量も特に限定されず、第１発明の燃焼触媒において説明した方法及び量に倣って設定できる。
【００４６】
珪酸カルシウムと銅塩との反応により、第１発明の燃焼触媒において説明したような反応生成物、即ちカルシウム塩、非晶質シリカ及び銅化合物を含む反応生成物が得られる。
【００４７】
珪酸カルシウムに対して反応当量未満の銅塩を用いた場合には、反応生成物に未反応珪酸カルシウムが残存する場合があるが触媒性能上支障はない。珪酸カルシウム成形体の表層部だけが銅塩と反応した場合でも触媒性能上支障はない。
【００４８】
次いで、反応生成物を焼成する。焼成条件は特に限定されないが、通常、酸化雰囲気又は大気中１５０〜８００℃、好ましくは５００〜８００℃で焼成すればよい。焼成時間も特に限定されないが、通常１〜１０時間、好ましくは２〜８時間程度である。焼成により、反応生成物が一旦収縮するため、後に高温下で燃焼触媒として使用した際の収縮を抑制できる。
【００４９】
焼成条件によってはカルシウム塩がわずかに溶融・分解したり、カルシウム酸化物が生成する場合がある。銅酸化物に完全に変化しなかった銅化合物が不可避的に残存したり、焼成される過程で銅化合物から銅塩が生成する場合がある。非晶質シリカの一部が結晶質シリカに転移する場合がある。これらの場合も、触媒性能上特に支障はない。
【００５０】
前記で説明した方法により得られる燃焼触媒中の所定成分の含有割合は特に限定的ではないが、燃焼触媒１００重量％中、通常、結晶質シリカ及び非晶質シリカの少なくとも１種０．５〜３０重量％程度（なお結晶質シリカ及び非晶質シリカの割合は特に限定されない）、カルシウム塩１〜５５重量％程度、銅酸化物２〜８５重量％程度である。但し、各成分の含有割合は、燃焼触媒の所望の性能等に応じて適宜設定でき、必ずしも上記範囲に限定されない。
【００５１】
反応生成物の成形方法としては特に限定されず、第１発明の燃焼触媒において説明した方法が採用できる。なお、焼成は成形の前後いずれに行ってもよい。
【００５２】
第４発明の自動車排ガス浄化用燃焼触媒
第４発明の燃焼触媒は、結晶質シリカ及び非晶質シリカの少なくとも１種並びに銅酸化物を含む。
【００５３】
燃焼触媒中の結晶質シリカ及び非晶質シリカの少なくとも１種並びに銅酸化物の含有割合は特に限定されず、用いる原料の種類等に応じて異なるが、例えば、後記の製造方法で示した範囲から、最終製品の目的、所望の性能等に応じて適宜設定できる。
【００５４】
燃焼触媒には、上記２成分（結晶質シリカ及び非晶質シリカはまとめてシリカ１成分とする）の他、燃焼触媒活性を妨げない範囲において添加剤が含まれていてもよい。添加剤としては特に限定されず、燃焼触媒の分野で公知のものが使用できる。添加剤の種類、配合量等は、最終製品の目的、所望の性能等に応じて適宜設定できる。
【００５５】
製造方法
燃焼触媒の製造方法としては、
（１）珪酸カルシウムと銅塩（ＣｕＣ ２ Ｏ ４ ・１／２Ｈ ２ Ｏ）とを反応させて得られた反応生成物を水洗するか、又は酸処理もしくは銅塩水溶液による処理を経て水洗した後、更に焼成する方法、又は
（２）珪酸カルシウムと銅塩（ＣｕＣ ２ Ｏ ４ ・１／２Ｈ ２ Ｏ）とを反応させて得られた反応生成物を焼成後、更に水洗するか、又は酸処理もしくは銅塩水溶液による処理を経て水洗する方法、
を用いる。以下、これらの製造方法について説明する。
【００５６】
珪酸カルシウム及び銅塩（ＣｕＣ ２ Ｏ ４ ・１／２Ｈ ２ Ｏ）としては特に限定されず、第１発明の燃焼触媒において説明したものと同じものが使用できる。
【００５７】
珪酸カルシウムと銅塩とを反応させる方法及び珪酸カルシウムと反応させる銅塩の量も特に限定されず、第１発明の燃焼触媒において説明した方法及び量に倣って設定できる。
【００５８】
珪酸カルシウムと銅塩との反応により、第１発明の燃焼触媒において説明したような反応生成物、即ちカルシウム塩、非晶質シリカ及び銅化合物を含む反応生成物が得られる。
【００５９】
珪酸カルシウムに対して反応当量未満の銅塩を用いた場合には、反応生成物に未反応珪酸カルシウムが残存する場合があるが触媒性能上支障はない。珪酸カルシウム成形体の表層部だけが銅塩と反応した場合でも触媒性能上支障はない。
【００６０】
（１）の方法では、珪酸カルシウムと銅塩との反応後、反応生成物を水洗するか、又は酸処理もしくは銅塩水溶液による処理を経て水洗した後、更に焼成する。
【００６１】
水洗、又は酸処理もしくは銅塩水溶液による処理条件としては、第２発明の燃焼触媒において説明した条件が採用できる。水洗、又は酸処理もしくは銅塩水溶液による処理条件によっては、不可避的にわずかなカルシウム塩が残存する場合があるが、触媒性能上特に支障はない。
【００６２】
焼成条件としては、第３発明の燃焼触媒において説明した条件が採用できる。焼成条件によっては、銅酸化物に完全に変化しなかった銅化合物が不可避的に残存したり、焼成過程で銅化合物から銅塩が生成する場合がある。また、非晶質シリカの一部が結晶質シリカに転移する場合がある。いずれの場合も触媒性能上支障はない。
【００６３】
（２）の方法では、珪酸カルシウムと銅塩との反応後、反応生成物を焼成後、更に水洗するか、又は酸処理もしくは銅塩水溶液による処理を経て水洗する。
【００６４】
焼成条件、水洗、又は酸処理もしくは銅塩水溶液による処理条件については、上記（１）の方法において説明した条件と同じである。（２）の方法の場合にも、カルシウム塩及び銅化合物の残存、非晶質シリカの結晶質シリカへの転移等が生じる場合がある。いずれの場合も触媒性能上支障はない。
【００６５】
前記（１）及び（２）の方法により得られる燃焼触媒中の所定成分の含有割合は特に限定的ではないが、燃焼触媒１００重量％中、通常、結晶質シリカ及び非晶質シリカの少なくとも１種０．５〜４５重量％程度（なお結晶質シリカ及び非晶質シリカの割合は特に限定されない）、銅酸化物３〜９５重量％程度である。但し、各成分の含有割合は、燃焼触媒の所望の性能等に応じて適宜設定でき、必ずしも上記範囲に限定されない。
【００６６】
反応生成物の成形方法としては特に限定されず、第１発明の燃焼触媒において説明した方法が採用できる。なお、水洗、又は酸処理もしくは銅塩水溶液による処理は成形の前に行う方が好ましい。
【００６７】
燃焼触媒の使用態様
本発明の燃焼触媒は、自動車排ガスの浄化用である。特に自動車排ガス中の一酸化炭素及び／又は未燃炭化水素の浄化用として好適に適用できる。未燃炭化水素としては、例えば、アセチレン、エタン、プロパン、プロピレン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン等が挙げられる。
【００６８】
本発明の燃焼触媒は、自動車排ガス成分の中でも、特に一酸化炭素及び／又はプロピレンを二酸化炭素及び／又は水に転化する用途に好適に使用できる。本発明の燃焼触媒は、通常１５０〜９００℃において排ガス（特に、一酸化炭素及び／又はプロピレン）浄化活性を発揮するが、特に４００〜８００℃において高い排ガス浄化活性を発揮する。
【００６９】
本発明の燃焼触媒の形状は特に限定されず、使用態様に応じて適宜設定できる。例えば、成形体（棒状、板状、ハニカム状等）でもよく、粉末状でもよく、粒状でもよい。抄造により紙状、シート状等に成形してもよく、これらの積層体にしてもよい。
【００７０】
成形体にする場合には、燃焼触媒に有機繊維、無機繊維等を配合してもよい。これにより、成形体の保形性、強度等を向上させることができる。
【００７１】
本発明の燃焼触媒の使用方法は、本発明の燃焼触媒と排ガスとを接触させることができる限り特に限定されず、既存の排ガス燃焼触媒の使用方法に倣って使用することもできる。例えば、粉末状又は粒状の燃焼触媒を反応管に充填してなる充填体に排ガスを流通させ、燃焼触媒と排ガスとを接触させればよい。より具体的には、そのような充填体を触媒コンバーター又はその他の排ガスの流路に設置すればよい。必要に応じて、ハニカム等に固定して使用してもよい。固定方法等は特に限定されず、公知の方法に従えばよい。
【作用】
【００７２】
加熱下において、本発明の燃焼触媒に自動車排ガスが接触すると、自動車排ガスが酸化燃焼により浄化される。具体的には、自動車排ガス成分、特に一酸化炭素及び／又は未燃炭化水素（特にプロピレン）が燃焼分解されて二酸化炭素及び／又は水に転化する。このような燃焼触媒効果は、長期にわたり維持できる。
【発明の効果】
【００７３】
本発明の燃焼触媒は、貴金属を主たる活性成分とした既存の燃焼触媒と比較して、安価である。また排ガス浄化活性も高いものである。特に、４００〜８００℃において、自動車排ガス中の一酸化炭素及び／又は未燃炭化水素（特にプロピレン）を浄化する能力が高い。
【実施例】
【００７４】
以下に実施例及び参考例を示し、本発明をより具体的に説明する。但し、本発明は実施例に限定されるものではない。
【００７５】
実施例１（第１、３発明の燃焼触媒）
（１）ゾノトライト球状二次粒子からなる合成珪酸カルシウムの水性スラリー３４９ｇ（固形分３０ｇ）にシュウ酸銅懸濁液（ＣｕＣ２Ｏ４・１／２Ｈ２Ｏ：５２ｇ、水：２０００ｇ）を加えて、８０℃で２０時間攪拌（１５０ｒｐｍ）して反応させた。反応後のスラリーを吸引濾過し、固形分を１０５℃において１２時間乾燥させた。これにより、シュウ酸カルシウム、非晶質シリカ及びＸ線回折図形の２θ＝２３．５°付近及び２θ＝３１．０°付近にピークを有する銅化合物を含む燃焼触媒を得た。
（２）得られた燃焼触媒を８ＭＰａの圧力で成形後に粉砕し、ふるいにより粒径１．２〜４ｍｍの粒状燃焼触媒を得た。
（３）得られた粒状燃焼触媒（触媒１）と、それを大気中５００℃、７００℃でそれぞれ４時間焼成して得られた粒状燃焼触媒との合計３種類について、下記の試験例に示した方法により、下記表２に示す自動車排ガス（モデルガス）中の一酸化炭素及びプロピレンの浄化率（分解率）を算出した。結果を下記表１に示す。
【００７６】
なお、５００℃で焼成して得られた粒状燃焼触媒（触媒２）は、酸化銅、炭酸カルシウム及び非晶質シリカから構成されていた。７００℃で焼成して得られた粒状燃焼触媒（触媒３）は、酸化銅、酸化カルシウム及び非晶質シリカから構成されていた。
【００７７】
試験例
触媒１〜３を２０ｇずつ秤量して、それぞれ図２に示す反応管に入れた。下記表２に示す成分のモデルガスを流量２５．７ｌ／ｍｉｎで反応管に流しながら、反応管を室温から４５０℃まで昇温速度２０℃／ｍｉｎで加熱した。４５０℃に達した時の反応管出口側から排出される各ガス濃度をガスクロマトグラフィーにより分析して、下記式より一酸化炭素及びプロピレンの浄化率を算出した。
＊ 浄化率（％）＝｛１−Ｃ１／Ｃ０｝×１００
Ｃ０：反応管入口側から導入される一酸化炭素又はプロピレンのガス濃度
Ｃ１：反応管出口側から排出される一酸化炭素又はプロピレンのガス濃度
【００７８】
【表１】
【表２】
実施例２（第２、４発明の燃焼触媒）
（１）実施例１の（１）で得られた反応後のスラリーを吸引濾過し、固形分を硫酸銅水溶液（ＣｕＳＯ４・５Ｈ２Ｏ：１３８．４ｇ、水：２０００ｇ）と接触させた。次いで、固形分を中性になるまで水洗することにより、シュウ酸カルシウム分を除去した。次いで、固形分を１０５℃において１２時間乾燥させた。これにより、非晶質シリカ、シュウ酸銅及び塩基性硫酸銅（Ｃｕ４ＳＯ４（ＯＨ）６）を含む燃焼触媒を得た。
（２）得られた燃焼触媒を８ＭＰａの圧力で成形後に粉砕し、ふるいにより粒径１．２〜４ｍｍの粒状燃焼触媒を得た。
（３）得られた粒状燃焼触媒（触媒４）と、それを大気中５００℃、７００℃でそれぞれ４時間焼成して得られた粒状燃焼触媒との合計３種類について、上記の試験例に示した方法により、上記表２に示すモデルガス中の一酸化炭素及びプロピレンの浄化率を算出した。結果を下記表３に示す。
【００８１】
なお、５００℃で焼成して得られた粒状燃焼触媒（触媒５）及び７００℃で焼成して得られた粒状燃焼触媒（触媒６）は、いずれも酸化銅及び非晶質シリカから構成されていた。
【００８２】
【表３】
参考例１
（１）ゾノトライト球状二次粒子からなる合成珪酸カルシウムの水性スラリー１０７０ｇ（固形分８９．２ｇ）に、硫酸銅水溶液（ＣｕＳＯ４・５Ｈ２Ｏ：３９．３ｇ、水：１０００ｇ）を加えて、２０℃で１時間攪拌（２５０ｒｐｍ）して反応させた。反応後のスラリーを吸引濾過し、固形分を中性になるまで水洗後、固形分を１０５℃において１２時間乾燥させた。これにより、塩基性硫酸銅（Ｃｕ４ＳＯ４（ＯＨ）６）及び非晶質シリカを含む燃焼触媒を得た。
（２）得られた燃焼触媒を８ＭＰａの圧力で成形後に粉砕し、ふるいにより粒径１．２〜４ｍｍの粒状燃焼触媒を得た。
（３）得られた粒状燃焼触媒（触媒７）と、それを大気中５００℃で４時間焼成して得られた粒状燃焼触媒との合計２種類について、上記の試験例に示した方法により、上記表２に示すモデルガス中の一酸化炭素及びプロピレンの浄化率を算出した。結果を下記表４に示す。
【００８４】
なお、５００℃で焼成して得られた粒状燃焼触媒（触媒８）は、酸化銅、銅酸化物（Ｃｕ２Ｏ（ＳＯ４））、硫酸銅及び非晶質シリカから構成されていた。
【００８５】
【表４】
参考例２
（１）トバモライト球状二次粒子からなる合成珪酸カルシウムの水性スラリー７５０ｇ（固形分５０ｇ）に、硝酸銅水溶液（（Ｃｕ（ＮＯ３）２・３Ｈ２Ｏ：１０７．６ｇ、水：２０００ｇ）を加えて、２０℃で１時間攪拌（２５０ｒｐｍ）して反応させた。反応後のスラリーを吸引濾過し、中性になるまで水洗後、固形物を１０５℃において１２時間乾燥させた。これにより、塩基性硝酸銅（Ｃｕ２（ＯＨ）３ＮＯ３）、非晶質シリカ及び少量の合成珪酸カルシウム（トバモライト）を含む燃焼触媒を得た。
（２）得られた燃焼触媒を８ＭＰａの圧力で成形後に粉砕し、ふるいにより粒径１．２〜４ｍｍの粒状燃焼触媒を得た。
（３）得られた粒状燃焼触媒（触媒９）と、それを大気中５００℃、７００℃でそれぞれ４時間焼成して得られた粒状燃焼触媒との合計３種類について、上記の試験例に示した方法により、上記表２に示すモデルガス中の一酸化炭素及びプロピレンの浄化率を算出した。結果を下記表５に示す。
【００８７】
なお、５００℃で焼成して得られた粒状燃焼触媒（触媒１０）は、酸化銅、α−石英（結晶質シリカ）及び少量の合成珪酸カルシウム（トバモライト）から構成されていた。７００℃で焼成して得られた粒状燃焼触媒（触媒１１）は、酸化銅、α−石英及び少量のβ−ワラストナイトから構成されていた。
【００８８】
【表５】
【図面の簡単な説明】
【図１】実施例１で得られた粒状燃焼触媒のＸ線回折図である。
【図２】実施例及び参考例の試験例で用いた反応管の模式図である。[0001]
BACKGROUND OF THE INVENTION
[0002]
The present invention relates to an automobile exhaust gas purification combustion catalyst. Motor vehicles in this specification also include motorcycles and motorbikes.
[Prior art]
[0003]
Conventionally, various combustion catalysts for purifying automobile exhaust gas have been developed. For example, a combustion catalyst is known in which a noble metal such as platinum, rhodium or palladium having catalytic activity is supported on a support such as alumina.
[0004]
Specifically, for example, in Patent Document 1, a first coat layer mainly composed of activated alumina containing at least one kind of noble metal selected from the group consisting of platinum, palladium and rhodium is provided on a catalyst carrier. In addition, a second coat layer made of an inorganic substance mainly composed of activated alumina not containing a noble metal component is provided on the first coat layer, and an inorganic substance mainly composed of zeolite powder obtained by ion exchange of metal on the second coat layer. An exhaust gas purifying catalyst is disclosed in which a catalyst having a third coat layer made of is disposed on the upstream side of the catalytic converter, and a three-way catalyst is disposed on the downstream side of the converter.
[0005]
Among existing combustion catalysts, it is known that a combustion catalyst having a noble metal as an active component as described above has high exhaust gas purification activity. However, such a combustion catalyst has a problem that the cost is high because the noble metal component is expensive. In particular, when alumina or the like is used as the carrier, the cost of the combustion catalyst is further increased.
[0006]
Therefore, development of a combustion catalyst that is less expensive than conventional products and has high exhaust gas purification activity is desired.
[Patent Document 1]
JP 7-256113 A
[Problems to be solved by the invention]
[0007]
The main object of the present invention is to provide a combustion catalyst that is less expensive than conventional products and has high exhaust gas purification activity.
[Means for Solving the Problems]
[0008]
As a result of intensive studies to achieve the above object, the present inventor,Calcium silicate and CuC 2 O 4 ・ 1 / 2H 2 Obtained through a step of reacting with O,The inventors have found that a material comprising a specific inorganic material and a copper compound can achieve the above object, and have completed the present invention.
[0009]
That is, the present invention relates to the following automobile exhaust gas purification combustion catalyst and method for producing the same.
1. Calcium silicate and CuC 2 O 4 ・ 1 / 2H 2 A combustion catalyst for purifying automobile exhaust gas, comprising calcium salt, amorphous silica and copper compound obtained by reacting with O (first invention).
2. Calcium silicate and CuC 2 O 4 ・ 1 / 2H 2 An automobile characterized by containing amorphous silica and a copper compound obtained by washing a reaction product obtained by reacting with O with water, or washing with water through acid treatment or treatment with an aqueous copper salt solution. A combustion catalyst for purifying exhaust gas (second invention).
3. Calcium silicate and CuC 2 O 4 ・ 1 / 2H 2 The reaction product obtained by reacting with O A combustion catalyst for purifying automobile exhaust gas, comprising at least one of crystalline silica and amorphous silica, calcium salt and copper oxide obtained by firing (third invention).
4). Calcium silicate and CuC 2 O 4 ・ 1 / 2H 2 At least crystalline silica and amorphous silica obtained by washing the reaction product obtained by reacting with O with water, or by washing with water after acid treatment or treatment with an aqueous copper salt solution, at least A combustion catalyst for purifying automobile exhaust gas, comprising one type and copper oxide (fourth invention).
5. Calcium silicate and CuC 2 O 4 ・ 1 / 2H 2 At least one of crystalline silica and amorphous silica obtained by firing the reaction product obtained by reacting with O and further washing with water or by washing with acid treatment or treatment with an aqueous copper salt solution. A combustion catalyst for purifying automobile exhaust gas, comprising seeds and copper oxide (fourth invention).
6). Item 3. The combustion catalyst for purifying automobile exhaust gas according to Item 1 or 2, wherein the copper compound has peaks at 2θ = 23.5 ° and 2θ = 31.0 ° of the X-ray diffraction pattern.
7). Calcium silicate and CuC 2 O 4 ・ 1 / 2H 2 Item 2. The method for producing a combustion catalyst for purifying automobile exhaust gas according to Item 1, wherein O is reacted.
8). Calcium silicate and CuC 2 O 4 ・ 1 / 2H 2 3. The method for producing a combustion catalyst for purifying automobile exhaust gas according to item 2, wherein the reaction product obtained by reacting with O is washed with water or washed with acid treatment or treatment with an aqueous copper salt solution. .
9. Calcium silicate and CuC 2 O 4 ・ 1 / 2H 2 Item 4. The method for producing a combustion catalyst for purifying automobile exhaust gas according to Item 3, wherein a reaction product obtained by reacting with O is calcined.
10. Calcium silicate and CuC 2 O 4 ・ 1 / 2H 2 The reaction product obtained by reacting with O is washed with water, or after being washed with an acid treatment or a treatment with an aqueous copper salt solution, and then further calcinated, for purifying automobile exhaust gas according to item 4 above A method for producing a combustion catalyst.
11. Calcium silicate and CuC 2 O 4 ・ 1 / 2H 2 The combustion product for purifying automobile exhaust gas according to item 5, wherein the reaction product obtained by reacting with O is fired and then washed with water, or after washing with acid treatment or treatment with an aqueous copper salt solution. A method for producing a catalyst.
DETAILED DESCRIPTION OF THE INVENTION
[0010]
Combustion catalyst for purifying automobile exhaust gas of the first invention
The combustion catalyst of the first invention includes a calcium salt, amorphous silica and a copper compound.
[0011]
BurningThe content ratio of the calcium salt, amorphous silica and copper compound in the firing catalyst is not particularly limited and varies depending on the type of raw material used, but for example, from the range shown in the production method described later, the purpose of the final product It can be appropriately set according to the desired performance.
[0012]
In addition to the above three components, the combustion catalyst may contain additives in a range that does not interfere with the combustion catalyst activity. The additive is not particularly limited, and those known in the field of combustion catalysts can be used. The type and amount of additives can be appropriately set according to the purpose of the final product, desired performance, and the like.
[0013]
Production method
As a manufacturing method of combustion catalyst, SilicaCalcium and copper salts(CuC 2 O 4 ・ 1 / 2H 2 O)To react withUse. Hereinafter, this manufacturing method will be described.
[0014]
The calcium silicate is not particularly limited and may be either synthetic calcium silicate or natural calcium silicate, but synthetic calcium silicate is preferable in consideration of reactivity, moldability, and the like.
[0015]
Synthetic calcium silicate is obtained by hydrothermal reaction from a lime raw material and a silicic acid raw material, for example, zonotlite, tobermorite, foshygite, gyrolite, α-dicalcium silicate, tricalcium silicate, millebrandite, Examples include Rosenhanite, Truscotite, Lierite, Calcio Chondrodite, Killcoreite, Affilite. Further, synthetic calcium silicate hydrates such as quasicrystalline calcium silicate (CSHn), wollastonite obtained by heating synthetic calcium silicate hydrates such as the above-mentioned zonotlite and tobermorite, and the like are also included.
[0016]
As a copper salt, CuC2O4・ 1 / 2H2O (copper oxalate)Use. When copper oxalate is used, a combustion catalyst having high exhaust gas purification activity is easily obtained.
[0017]
The method for reacting calcium silicate and copper salt is not particularly limited. For example, a method of mixing a copper salt into an aqueous slurry of calcium silicate, a method of impregnating a calcium silicate molded body with a copper salt solution, a method of mixing a calcium silicate powder into a copper salt solution, and the like.
[0018]
The amount of the copper salt to be reacted with calcium silicate is not particularly limited, and can be appropriately set in consideration of the purpose of the final product, desired performance, and the like. The amount of the copper salt may be a reaction equivalent with respect to calcium silicate, an amount exceeding it, or less than an equivalent.
[0019]
Calcium silicate and copper salt(CuC 2 O 4 ・ 1 / 2H 2 O)By reaction with, CaC2O4・ H2O, CaC2O4A copper compound having peaks in the vicinity of 2θ = 23.5 ° and 2θ = 31.0 ° of the X-ray diffraction pattern as shown in FIG. 1 is obtained.
[0020]
When a copper salt having a reaction equivalent to that of calcium silicate is used, unreacted calcium silicate may remain in the reaction product, but there is no problem in catalyst performance. Even when only the surface layer portion of the calcium silicate molded body reacts with the copper salt, there is no problem in the catalyst performance.
[0021]
The reaction product thus obtained (when the calcium silicate powder is reacted with the copper salt solution, obtained by filtering the suspension after the reaction) is molded as necessary. A combustion catalyst containing a predetermined calcium salt, amorphous silica, and copper compound can be obtained by making it into a desired shape by, for example, drying as necessary.
[0022]
The content ratio of the predetermined component in the combustion catalyst obtained by the method described above is not particularly limited, but is usually about 1 to 50% by weight of calcium salt and 1 to 30% of amorphous silica in 100% by weight of the combustion catalyst. About 2% by weight and about 2 to 85% by weight of the copper compound. However, the content ratio of each component can be appropriately set according to the desired performance of the combustion catalyst, and is not necessarily limited to the above range.
[0023]
Although it does not specifically limit as a shaping | molding method of a reaction product, For example, a press molding method, an extrusion molding method, a mold shaping method, a papermaking method, a granulation method etc. are mentioned. If necessary, it may be heated during molding, or may be dried, steam-cured, etc. after molding. Further, the molded body may be pulverized into a powder form.
[0024]
Combustion catalyst for purifying automobile exhaust gas of the second invention
The combustion catalyst of the second invention contains amorphous silica and a copper compound.
[0025]
BurningThe content ratio of the amorphous silica and the copper compound in the firing catalyst is not particularly limited, and varies depending on the type of raw material used. For example, from the range shown in the production method described later, the purpose of the final product, desired It can be set as appropriate according to performance and the like.
[0026]
In addition to the above two components, the combustion catalyst may contain additives in a range that does not interfere with the combustion catalyst activity. The additive is not particularly limited, and those known in the field of combustion catalysts can be used. The type and amount of additives can be appropriately set according to the purpose of the final product, desired performance, and the like.
[0027]
Production method
As a manufacturing method of combustion catalyst, SilicaCalcium and copper salts (CuC 2 O 4 ・ 1 / 2H 2 O)A method of washing the reaction product obtained by reacting with water, or washing with water through acid treatment or treatment with an aqueous copper salt solutionUse. Hereinafter, this manufacturing method will be described.
[0028]
Calcium silicate and copper salt (CuC 2 O 4 ・ 1 / 2H 2 O)There is no particular limitation, and the same materials as those described in the combustion catalyst of the first invention can be used.
[0029]
The method of reacting calcium silicate and copper salt and the amount of copper salt reacted with calcium silicate are not particularly limited, and can be set according to the method and amount described in the combustion catalyst of the first invention.
[0030]
By the reaction of calcium silicate and copper salt, a reaction product as described in the combustion catalyst of the first invention, that is, a reaction product containing calcium salt, amorphous silica and copper compound is obtained.
[0031]
When a copper salt having a reaction equivalent to that of calcium silicate is used, unreacted calcium silicate may remain in the reaction product, but there is no problem in catalyst performance. Even when only the surface layer portion of the calcium silicate molded body reacts with the copper salt, there is no problem in the catalyst performance.
[0032]
Next, the reaction product is washed with water, or washed with an acid treatment or a treatment with an aqueous copper salt solution. Conditions for washing with water, or acid treatment or treatment with an aqueous copper salt solution are not particularly limited as long as the calcium salt contained in the reaction product can be sufficiently solubilized and removed.
[0033]
When washing with water, the reaction product may be brought into contact with water.
[0034]
For the acid treatment, for example, an acid treatment solution such as sulfuric acid, nitric acid, hydrochloric acid, and acetic acid can be used. Although the density | concentration of an acid treatment liquid is not specifically limited, Usually, 1-12 N, Preferably it is about 3-8 N. What is necessary is just to make a reaction product and an acid treatment liquid contact in the case of an acid treatment.
[0035]
For the treatment with an aqueous copper salt solution, for example, an aqueous solution of copper sulfate, nitrate, acetate, chloride or the like can be used. Although the density | concentration of copper salt aqueous solution is not specifically limited, Usually, 2 to 30 weight%, Preferably it is about 3 to 10 weight%. What is necessary is just to make a reaction product and the said aqueous solution contact in the case of a process.
[0036]
These acid treatment or treatment with an aqueous copper salt solution is effective when, for example, copper oxalate is used as a copper salt to be reacted with calcium silicate. The reason for this is as follows. Since calcium oxalate obtained by the reaction between copper oxalate and calcium silicate is hardly soluble in water, calcium oxalate cannot be sufficiently removed only by washing with water. However, this is because, if the calcium oxalate is changed to water-soluble calcium sulfate by acid treatment or treatment with an aqueous copper salt solution, for example, contact with an aqueous copper sulfate solution, this can be removed by subsequent water washing..
[0037]
ThisAfter the acid treatment or the treatment with the copper salt aqueous solution, the reaction product is washed with water. It is preferable to wash with water until neutrality is obtained. Depending on these treatment conditions, a slight amount of calcium salt may inevitably remain in the reaction product, but there is no particular problem in catalyst performance.
[0038]
The content ratio of the predetermined component in the combustion catalyst obtained by the above-described method is not particularly limited, but is usually about 0.5 to 40% by weight of amorphous silica in 100% by weight of the combustion catalyst, and the copper compound 3 About 95% by weight. However, the content ratio of each component can be appropriately set according to the desired performance of the combustion catalyst, and is not necessarily limited to the above range.
[0039]
The method for forming the reaction product is not particularly limited, and the method described in the combustion catalyst of the first invention can be adopted. However, washing with water, or acid treatment or treatment with an aqueous copper salt solution is preferably performed before molding.
[0040]
Combustion catalyst for purification of automobile exhaust gas according to the third invention
The combustion catalyst of the third invention includes at least one of crystalline silica and amorphous silica, calcium salt and copper oxide..
[0041]
BurningThe content ratio of at least one of crystalline silica and amorphous silica, calcium salt, and copper oxide in the firing catalyst is not particularly limited, and varies depending on the type of raw material used. From the range shown, it can be set as appropriate according to the purpose of the final product, desired performance, and the like.
[0042]
In addition to the above three components (crystalline silica and amorphous silica are collectively used as one component of silica), the combustion catalyst may contain additives in a range that does not interfere with the combustion catalyst activity. The additive is not particularly limited, and those known in the field of combustion catalysts can be used. The type and amount of additives can be appropriately set according to the purpose of the final product, desired performance, and the like.
[0043]
Production method
As a manufacturing method of combustion catalyst, SilicaCalcium and copper salts (CuC 2 O 4 ・ 1 / 2H 2 O)A method of firing a reaction product obtained by reactingUse. Hereinafter, this manufacturing method will be described.
[0044]
Calcium silicate and copper salt (CuC 2 O 4 ・ 1 / 2H 2 O)There is no particular limitation, and the same materials as those described in the combustion catalyst of the first invention can be used.
[0045]
The method of reacting calcium silicate and copper salt and the amount of copper salt reacted with calcium silicate are not particularly limited, and can be set according to the method and amount described in the combustion catalyst of the first invention.
[0046]
By the reaction of calcium silicate and copper salt, a reaction product as described in the combustion catalyst of the first invention, that is, a reaction product containing calcium salt, amorphous silica and copper compound is obtained.
[0047]
When a copper salt having a reaction equivalent to that of calcium silicate is used, unreacted calcium silicate may remain in the reaction product, but there is no problem in catalyst performance. Even when only the surface layer portion of the calcium silicate molded body reacts with the copper salt, there is no problem in the catalyst performance.
[0048]
Next, the reaction product is baked. The firing conditions are not particularly limited, but the firing is usually performed in an oxidizing atmosphere or in the air at 150 to 800 ° C., preferably 500 to 800 ° C. The firing time is not particularly limited, but is usually 1 to 10 hours, preferably about 2 to 8 hours. Since the reaction product shrinks once by firing, shrinkage when used as a combustion catalyst at a high temperature later can be suppressed.
[0049]
Depending on the firing conditions, the calcium salt may slightly melt and decompose, or calcium oxide may be generated. In some cases, a copper compound that has not completely changed to copper oxide remains unavoidably, or a copper salt may be generated from the copper compound in the process of firing. Some amorphous silica may be transferred to crystalline silica. In these cases, there is no particular problem in the catalyst performance.
[0050]
Although the content ratio of the predetermined component in the combustion catalyst obtained by the method described above is not particularly limited, it is usually at least one of crystalline silica and amorphous silica in 100% by weight of the combustion catalyst. About 30% by weight (the ratio of crystalline silica and amorphous silica is not particularly limited), about 1 to 55% by weight of calcium salt, and about 2 to 85% by weight of copper oxide. However, the content ratio of each component can be appropriately set according to the desired performance of the combustion catalyst, and is not necessarily limited to the above range.
[0051]
The method for forming the reaction product is not particularly limited, and the method described in the combustion catalyst of the first invention can be adopted. The firing may be performed before or after the molding.
[0052]
Combustion catalyst for purification of automobile exhaust gas of the fourth invention
The combustion catalyst of the fourth invention includes at least one of crystalline silica and amorphous silica and copper oxide..
[0053]
BurningThe content ratio of at least one kind of crystalline silica and amorphous silica and copper oxide in the firing catalyst is not particularly limited, and varies depending on the type of raw material used, for example, the range shown in the production method described later Therefore, it can be appropriately set according to the purpose of the final product, desired performance, and the like.
[0054]
In addition to the above two components (crystalline silica and amorphous silica are collectively referred to as a single component of silica), the combustion catalyst may contain additives within a range that does not interfere with the combustion catalyst activity. The additive is not particularly limited, and those known in the field of combustion catalysts can be used. The type and amount of additives can be appropriately set according to the purpose of the final product, desired performance, and the like.
[0055]
Production method
As a manufacturing method of combustion catalyst,
(1)Calcium silicate and copper salt (CuC 2 O 4 ・ 1 / 2H 2 O)A reaction product obtained by reacting with water, or after washing with water through an acid treatment or a treatment with an aqueous copper salt solution, followed by firing,Or
(2)Calcium silicate and copper salt (CuC 2 O 4 ・ 1 / 2H 2 O)After firing the reaction product obtained by reacting with the above, further washing with water, or washing with water through acid treatment or treatment with an aqueous copper salt solution,
Use. Hereinafter, these manufacturing methods will be described.
[0056]
Calcium silicate and copper salt (CuC 2 O 4 ・ 1 / 2H 2 O)There is no particular limitation, and the same materials as those described in the combustion catalyst of the first invention can be used.
[0057]
The method of reacting calcium silicate and copper salt and the amount of copper salt reacted with calcium silicate are not particularly limited, and can be set according to the method and amount described in the combustion catalyst of the first invention.
[0058]
By the reaction of calcium silicate and copper salt, a reaction product as described in the combustion catalyst of the first invention, that is, a reaction product containing calcium salt, amorphous silica and copper compound is obtained.
[0059]
When a copper salt having a reaction equivalent to that of calcium silicate is used, unreacted calcium silicate may remain in the reaction product, but there is no problem in catalyst performance. Even when only the surface layer portion of the calcium silicate molded body reacts with the copper salt, there is no problem in the catalyst performance.
[0060]
(1)In this method, after the reaction between calcium silicate and the copper salt, the reaction product is washed with water, or washed with an acid treatment or a treatment with an aqueous copper salt solution, and then further baked.
[0061]
The conditions described in the combustion catalyst of the second invention can be adopted as the conditions for washing with water, acid treatment or treatment with an aqueous copper salt solution. Depending on the conditions of washing with water or treatment with acid treatment or aqueous copper salt solution, unavoidable slight calcium salt may remain, but there is no particular problem in terms of catalyst performance.
[0062]
As the firing conditions, the conditions described in the combustion catalyst of the third invention can be adopted. Depending on the firing conditions, a copper compound that has not completely changed in the copper oxide may inevitably remain, or a copper salt may be generated from the copper compound during the firing process. In addition, part of amorphous silica may be transferred to crystalline silica. In either case, there is no hindrance in catalyst performance.
[0063]
(2)In this method, after the reaction between calcium silicate and copper salt, the reaction product is baked and then further washed with water, or washed with acid treatment or treatment with an aqueous copper salt solution.
[0064]
For firing conditions, washing with water, or treatment with acid treatment or aqueous copper salt solution,(1)The conditions are the same as those described in the method.(2)In the case of this method as well, there are cases where the calcium salt and the copper compound remain, the amorphous silica is transferred to crystalline silica, and the like. In either case, there is no hindrance in catalyst performance.
[0065]
Said(1)as well as(2)The content ratio of the predetermined component in the combustion catalyst obtained by the method is not particularly limited, but is usually 0.5 to 45% by weight of at least one of crystalline silica and amorphous silica in 100% by weight of the combustion catalyst. The degree (the ratio of crystalline silica and amorphous silica is not particularly limited) is about 3 to 95% by weight of copper oxide. However, the content ratio of each component can be appropriately set according to the desired performance of the combustion catalyst, and is not necessarily limited to the above range.
[0066]
The method for forming the reaction product is not particularly limited, and the method described in the combustion catalyst of the first invention can be adopted. In addition, it is more preferable to perform the water washing or the acid treatment or the treatment with the copper salt aqueous solution before the molding.
[0067]
Usage of combustion catalyst
The combustion catalyst of the present invention is for purification of automobile exhaust gas. In particular, it can be suitably applied for purifying carbon monoxide and / or unburned hydrocarbons in automobile exhaust gas. Examples of unburned hydrocarbons include acetylene, ethane, propane, propylene, butane, pentane, hexane, heptane, octane, and nonane.
[0068]
The combustion catalyst of the present invention can be suitably used for applications that convert carbon monoxide and / or propylene into carbon dioxide and / or water, among automotive exhaust gas components. The combustion catalyst of the present invention usually exhibits exhaust gas (especially carbon monoxide and / or propylene) purification activity at 150 to 900 ° C., but particularly exhibits high exhaust gas purification activity at 400 to 800 ° C.
[0069]
The shape of the combustion catalyst of the present invention is not particularly limited, and can be appropriately set according to the use mode. For example, it may be a molded body (rod shape, plate shape, honeycomb shape, etc.), powder shape, or granular shape. It may be formed into a paper shape, a sheet shape, or the like by papermaking, or may be a laminate of these.
[0070]
In the case of forming a molded body, an organic fiber, an inorganic fiber, or the like may be blended with the combustion catalyst. Thereby, the shape retention property, intensity | strength, etc. of a molded object can be improved.
[0071]
The method of using the combustion catalyst of the present invention is not particularly limited as long as the combustion catalyst of the present invention can be brought into contact with the exhaust gas, and can be used following the existing method of using the exhaust gas combustion catalyst. For example, the exhaust gas may be circulated through a packed body obtained by filling a reaction tube with a powdered or granular combustion catalyst, and the combustion catalyst and the exhaust gas may be brought into contact with each other. More specifically, such a filler may be installed in a catalytic converter or other exhaust gas flow path. If necessary, it may be fixed to a honeycomb or the like. The fixing method and the like are not particularly limited, and may be a known method.
[Action]
[0072]
When the automobile exhaust gas comes into contact with the combustion catalyst of the present invention under heating, the automobile exhaust gas is purified by oxidative combustion. Specifically, automobile exhaust gas components, particularly carbon monoxide and / or unburned hydrocarbons (especially propylene) are combusted and decomposed and converted into carbon dioxide and / or water. Such a combustion catalytic effect can be maintained over a long period of time.
【The invention's effect】
[0073]
The combustion catalyst of the present invention is less expensive than an existing combustion catalyst having a noble metal as a main active component. Moreover, the exhaust gas purification activity is also high. In particular, at 400 to 800 ° C., the ability to purify carbon monoxide and / or unburned hydrocarbons (particularly propylene) in automobile exhaust gas is high.
【Example】
[0074]
Examples belowAnd reference examplesThe present invention will be described more specifically. However, the present invention is not limited to the examples.
[0075]
Example 1 (combustion catalyst of the first and third inventions)
(1) Copper oxalate suspension (CuC) to 349 g (solid content 30 g) of an aqueous slurry of synthetic calcium silicate composed of zonotolite spherical secondary particles2O4・ 1 / 2H2O: 52 g, water: 2000 g) was added, and the mixture was reacted at 80 ° C. for 20 hours with stirring (150 rpm). The slurry after the reaction was subjected to suction filtration, and the solid content was dried at 105 ° C. for 12 hours. As a result, a combustion catalyst containing calcium oxalate, amorphous silica, and a copper compound having peaks in the vicinity of 2θ = 23.5 ° and 2θ = 31.0 ° of the X-ray diffraction pattern was obtained.
(2) The obtained combustion catalyst was pulverized after being molded at a pressure of 8 MPa, and a granular combustion catalyst having a particle size of 1.2 to 4 mm was obtained by sieving.
(3) The following test examples show the three types of the granular combustion catalyst (Catalyst 1) obtained and the granular combustion catalyst obtained by calcining it in the atmosphere at 500 ° C. and 700 ° C. for 4 hours, respectively. The purification rate (decomposition rate) of carbon monoxide and propylene in the automobile exhaust gas (model gas) shown in Table 2 below was calculated by the above method. The results are shown in Table 1 below.
[0076]
In addition, the granular combustion catalyst (catalyst 2) obtained by baking at 500 ° C. was composed of copper oxide, calcium carbonate, and amorphous silica. The granular combustion catalyst (catalyst 3) obtained by firing at 700 ° C. was composed of copper oxide, calcium oxide and amorphous silica.
[0077]
Test example
20 g of each of the catalysts 1 to 3 was weighed and placed in the reaction tube shown in FIG. The reaction tube was heated from room temperature to 450 ° C. at a heating rate of 20 ° C./min while flowing model gas of the components shown in Table 2 below at a flow rate of 25.7 l / min. The concentration of each gas discharged from the outlet side of the reaction tube when it reached 450 ° C. was analyzed by gas chromatography, and the purification rate of carbon monoxide and propylene was calculated from the following formula.
* Purification rate (%) = {1-C1/ C0} × 100
C0: Gas concentration of carbon monoxide or propylene introduced from the reaction tube inlet side
C1: Gas concentration of carbon monoxide or propylene discharged from the reaction tube outlet side
[0078]
[Table 1]
[Table 2]
Example 2 (Combustion catalyst of the second and fourth inventions)
(1) The slurry after the reaction obtained in (1) of Example 1 was suction filtered, and the solid content was converted to an aqueous copper sulfate solution (CuSOSO).4・ 5H2O: 138.4 g, water: 2000 g). Subsequently, the calcium oxalate content was removed by washing with water until the solid content became neutral. The solid was then dried at 105 ° C. for 12 hours. As a result, amorphous silica, copper oxalate and basic copper sulfate (Cu4SO4(OH)6) Was obtained.
(2) The obtained combustion catalyst was pulverized after being molded at a pressure of 8 MPa, and a granular combustion catalyst having a particle size of 1.2 to 4 mm was obtained by sieving.
(3) The above-mentioned test example shows a total of three types of the obtained granular combustion catalyst (catalyst 4) and the granular combustion catalyst obtained by calcining it at 500 ° C. and 700 ° C. for 4 hours in the atmosphere. The purification rate of carbon monoxide and propylene in the model gas shown in Table 2 was calculated by the above method. The results are shown in Table 3 below.
[0081]
The granular combustion catalyst (catalyst 5) obtained by firing at 500 ° C and the granular combustion catalyst (catalyst 6) obtained by firing at 700 ° C are both composed of copper oxide and amorphous silica. It was.
[0082]
[Table 3]
Reference example 1
(1) An aqueous copper sulfate solution (CuSO) was added to 1070 g (solid content 89.2 g) of an aqueous slurry of synthetic calcium silicate composed of spherical zonotlite spherical particles.4・ 5H2O: 39.3 g, water: 1000 g) was added, and the mixture was reacted at 20 ° C. for 1 hour with stirring (250 rpm). The slurry after the reaction was subjected to suction filtration, washed with water until the solid content became neutral, and then dried at 105 ° C. for 12 hours. As a result, basic copper sulfate (Cu4SO4(OH)6And a combustion catalyst containing amorphous silica.
(2) The obtained combustion catalyst was pulverized after being molded at a pressure of 8 MPa, and a granular combustion catalyst having a particle size of 1.2 to 4 mm was obtained by sieving.
(3) With respect to a total of two types of the obtained granular combustion catalyst (catalyst 7) and the granular combustion catalyst obtained by calcining it at 500 ° C. for 4 hours in the atmosphere, by the method shown in the above test example, The purification rates of carbon monoxide and propylene in the model gas shown in Table 2 were calculated. The results are shown in Table 4 below.
[0084]
In addition, the granular combustion catalyst (catalyst 8) obtained by firing at 500 ° C. is composed of copper oxide, copper oxide (Cu2O (SO4)), Copper sulfate and amorphous silica.
[0085]
[Table 4]
Reference example 2
(1) An aqueous copper nitrate solution (Cu (NO (NO)) is added to 750 g of an aqueous slurry of synthetic calcium silicate composed of tobermorite spherical secondary particles (solid content 50 g).3)2・ 3H2O: 107.6 g, water: 2000 g) was added, and the mixture was reacted at 20 ° C. for 1 hour (250 rpm). The slurry after the reaction was subjected to suction filtration, washed with water until neutral, and the solid was dried at 105 ° C. for 12 hours. As a result, basic copper nitrate (Cu2(OH)3NO3), A combustion catalyst containing amorphous silica and a small amount of synthetic calcium silicate (tobermorite) was obtained.
(2) The obtained combustion catalyst was pulverized after being molded at a pressure of 8 MPa, and a granular combustion catalyst having a particle size of 1.2 to 4 mm was obtained by sieving.
(3) The above-mentioned test example shows a total of three kinds of the obtained granular combustion catalyst (catalyst 9) and the granular combustion catalyst obtained by calcining it at 500 ° C. and 700 ° C. for 4 hours in the atmosphere. The purification rate of carbon monoxide and propylene in the model gas shown in Table 2 was calculated by the above method. The results are shown in Table 5 below.
[0087]
The granular combustion catalyst (catalyst 10) obtained by firing at 500 ° C. was composed of copper oxide, α-quartz (crystalline silica) and a small amount of synthetic calcium silicate (tobermorite). The granular combustion catalyst (catalyst 11) obtained by firing at 700 ° C. was composed of copper oxide, α-quartz and a small amount of β-wollastonite.
[0088]
[Table 5]
[Brief description of the drawings]
1 is an X-ray diffraction pattern of a granular combustion catalyst obtained in Example 1. FIG.
FIG. 2 ExampleAnd reference examplesIt is a schematic diagram of the reaction tube used in the test example.
Claims (11)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003122622A JP4032248B2 (en) | 2003-04-25 | 2003-04-25 | Combustion catalyst for automobile exhaust gas purification |
| US10/827,058 US7462576B2 (en) | 2003-04-25 | 2004-04-19 | Automobile exhaust gas purifying combustion catalysts |
| DE102004018847.5A DE102004018847B4 (en) | 2003-04-25 | 2004-04-19 | Automotive exhaust gas purifying combustion catalysts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003122622A JP4032248B2 (en) | 2003-04-25 | 2003-04-25 | Combustion catalyst for automobile exhaust gas purification |
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| JP2004322000A JP2004322000A (en) | 2004-11-18 |
| JP4032248B2 true JP4032248B2 (en) | 2008-01-16 |
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| JP2003122622A Expired - Fee Related JP4032248B2 (en) | 2003-04-25 | 2003-04-25 | Combustion catalyst for automobile exhaust gas purification |
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| US (1) | US7462576B2 (en) |
| JP (1) | JP4032248B2 (en) |
| DE (1) | DE102004018847B4 (en) |
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| CN119793471B (en) * | 2025-01-07 | 2025-07-04 | 东北电力大学 | A Cu-CaO@SiO2 core-shell catalyst for extracting silicon and calcium from waste stone powder, and its preparation method and application |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3981923A (en) * | 1969-06-11 | 1976-09-21 | Shell Oil Company | Dehydrogenation of alcohols to ketones |
| US4042313A (en) * | 1976-03-19 | 1977-08-16 | Philadelphia Quartz Company | Method of imparting color to fires |
| JPS5330995A (en) | 1976-09-03 | 1978-03-23 | Mitsubishi Heavy Ind Ltd | Catalyst for treating of exhaust gas |
| JPS5356164A (en) | 1976-11-01 | 1978-05-22 | Mitsubishi Chem Ind Ltd | Decomposing method for nitrogen oxides by catalytic reduction |
| JPS6017574B2 (en) | 1978-10-06 | 1985-05-04 | 松下電器産業株式会社 | Catalyst for gas purification |
| DE3123000C2 (en) | 1981-06-10 | 1984-04-05 | Klaus 2304 Stein Beneke | Process for the production of copper / copper oxide catalysts and their use |
| US5106810A (en) * | 1989-06-29 | 1992-04-21 | E. I. Du Pont De Nemours And Company | Methanol dissociation catalysts |
| JPH07256113A (en) | 1994-03-17 | 1995-10-09 | Nissan Motor Co Ltd | Exhaust gas purification catalyst |
| US5977010A (en) * | 1995-06-15 | 1999-11-02 | Engelhard Corporation | Shaped hydrogenation catalyst and processes for their preparation and use |
| FR2747053B1 (en) * | 1996-04-03 | 1998-10-02 | Rhone Poulenc Chimie | USE FOR THE DIRECT OXIDIZATION OF SULFUR AND / OR SULPHATES COMPOUNDS AT LOW TEMPERATURE FROM A COPPER BASED CATALYST |
| RU2106197C1 (en) | 1996-04-09 | 1998-03-10 | Институт катализа им.Г.К.Борескова СО РАН | Catalyst for cleaning gases from nitric oxides |
| JP2002371831A (en) | 2001-06-13 | 2002-12-26 | Nissan Diesel Motor Co Ltd | Exhaust emission control device of automobile |
-
2003
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2004
- 2004-04-19 US US10/827,058 patent/US7462576B2/en not_active Expired - Lifetime
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| DE102004018847A8 (en) | 2005-04-07 |
| DE102004018847A1 (en) | 2004-11-25 |
| US20040228784A1 (en) | 2004-11-18 |
| JP2004322000A (en) | 2004-11-18 |
| DE102004018847B4 (en) | 2023-07-06 |
| US7462576B2 (en) | 2008-12-09 |
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